Earliest research on carbon monoxide/hydrogen chemistry dates back to 1902 when Sabatier and Senderens passed CO and H.sub.2 (1:3) over reduced nickel at 1 atm and produced methane. It was reported by BASF in 1913 that at higher pressures (100-200 atm) and temperatures (300.degree.-400.degree. C.) the major products are liquids. Later in 1923 Fischer and Tropsch disclosed the use of alkalized iron turnings as catalysts for the production of an oily liquid from CO and H.sub.2 at 100-150 atm and 400.degree.-425.degree. C. This product contained mainly oxygenated compounds such as alcohols, acids, aldehydes, ketones and esters, and a very small quantity of hydrocarbons.
Continuing research with Fischer-Tropsch catalysts has lead to the development of commercial scale plants for methanol synthesis from carbon monoxide and hydrogen.
In 1949 Wender et al (J.A.C.S., 71, 4160) reported the homologation of alcohols by reaction with synthesis gas in the presence of a cobalt catalyst under oxo reaction conditions. There is described the conversion of t-butyl alcohol into isoamyl alcohol, and the conversion of benzyl alcohol into .beta.-phenylethyl alcohol. In 1951 these workers reported the conversion of methanol into ethanol under oxo reaction conditions with a cobalt catalyst. Other products of the reaction included methyl formate, methyl acetate, ethyl acetate, acetaldehyde, propyl alcohol, butyl alcohol and methane.
U.S. Pat. No. 2,623,906 discloses that at pressures above 1000 atmospheres, in the presence of a cobalt catalyst, primary, secondary and tertiary alcohols react with synthesis gas to form glycol ethers, and monohydric alcohols containing at least one more carbon atoms per molecule than the original alcohol reactant.
U.S. Pat. No. 3,285,948 discloses that an improved yield of ethanol from methanol can be obtained by conducting the synthesis gas homologation reaction in the presence of a cobalt catalyst which is promoted with iodine and a metal halide selected from ruthenium halide and osmium halide.
The prior art processes for homologation of alkanols are generally uneconomical because of the low selectivity of the catalyst systems and the concomitant large quantities of aldehydes, esters, acids and hydrocarbons which are produced and which are difficult to separate into individual components.
Accordingly, it is an object of this invention to provide an improved process for homologation of alkanols with carbon monoxide and hydrogen.
It is another object of this invention to provide a novel heterogeneous co-catalyst adapted for high efficiency conversion of methanol to ethanol and ethanol precursors.
It is a further object of this invention to provide a process for preparing an improved cobalt catalyst system for liquid phase homologation of alkanols.
Other objects and advantages of this invention shall become apparent from the following description and exemplary data.